The present invention relates to lubricating oil compositions and uses thereof containing a specific amount of the copolymer and the copolymer satisfying the specific requirements.
Background technique
[0002]Petroleum products has generally a viscosity greatly changes when the temperature changes, the temperature dependence of the so-called viscosity. The lubricating oil also has a temperature dependence of the viscosity, it is preferable that the temperature dependence of the viscosity is small. In order to reduce the temperature dependence of the viscosity, soluble polymers have been used in lubricating base oil as a viscosity index improver. Exemplary viscosity modifiers, mineral oil solution are known olefin copolymer or polymer of polymethacrylate (hereinafter PMA and description).
[0003]
　On the other hand, in recent years, from growing awareness of global environmental issues, development of products has been desired with reduced environmental impact in various industries. Such demand is no exception with respect to the lubricating oil composition, the lubricating oil compositions have been proposed having various biodegradable.
[0004]
　For example, lubricating oil compositions for grease and engine oils containing synthetic esters of vegetable oil or polyol such as soybean oil or rapeseed oil as a base oil has been proposed (e.g., see Non-Patent Document 1).
[0005]
　However, such a lubricating oil composition, as compared with conventional lubricating oil compositions, due to the low viscosity, the use range is limited.
[0006]
　The lubricating oil composition containing a vegetable oil as base oil, there is a problem in the storage characteristics and stability at low temperatures. In such a lubricating oil composition, when of containing a viscosity modifier such as OCP (olefin copolymer) type viscosity modifier, the viscosity modifier, poor solubility in vegetable oil, it is difficult to apply.
[0007]
　Furthermore, as a viscosity modifier in lubricating oil compositions in which the vegetable oil or synthetic ester as base oil, PMA by selecting the viscosity modifier (polymethacrylate) system, improve the solubility of the viscosity modifier in the base oil although the order PMA based viscosity modifier of the low biodegradability rate mineral that contain more than 50 wt% as a diluent oil, biodegradation rate of the lubricating oil composition is severely degraded.
[0008]
　On the other hand, Patent Document 1, an attempt using the ricinoleic acid polymer is disclosed as a viscosity modifier to be blended in the lubricating oil composition. Ricinoleic acid polymer as used in this patent document 1, only a homopolymer ricinoleic acid ester derivative, or a polymer obtained by copolymerizing ricinoleic acid ester derivatives with a hydroxy acid ester derivative. Then, Patent Document 1, by employing such a ricinoleic acid polymer as a viscosity modifier, as compared with the case of using the PMA based viscosity modifier, a lubricating oil composition to be obtained, equal to or greater than with exhibits viscosity characteristics (viscosity index improving effect) and frictional properties, it has been described to be excellent significantly biodegradable.
CITATION
Patent Document
[0009]
Patent Document 1: International Publication No. WO 2009/148110
Non-Patent Document
[0010]
Non-Patent Document 1: lubrication Jing Ji December 22 (2007)
Summary of the Invention
Problems that the Invention is to Solve
[0011]
　The present inventors have studied, the lubricating oil composition using ricinoleic acid polymer as a viscosity modifier, it was found new in which in terms of adhesive and discoloration resistance upon heating there is room for improvement . Normally, the lubricating oil composition, be heated is required to hardly discolored, also deposition maintain the sliding portion, it is desirable that a high adhesive strength to prevent sauce shatterproof -.
[0012]
　On the other hand, as the workability in preparing the lubricating oil composition, the solubility of the handling properties and the viscosity modifier to the base oil when charged viscosity modifier to the container is usually a tendency of more excellent intrinsic viscosity is smaller made, but it has been found that there is room for further improvement in handling properties and solubility in intrinsic viscosity commensurate.
[0013]
　Therefore, providing a while maintaining excellent biodegradability and viscosity characteristics of the lubricating oil composition using ricinoleic acid polymer, a lubricating oil composition excellent in the adhesiveness heat resistance (heat when discoloration inhibition) There is a challenge. Further, possible to provide such a lubricating oil composition, further provides handling properties and polymers that can be used as a viscosity modifier having excellent solubility in base oil in making a lubricating oil composition it is an object.
Means for Solving the Problems
[0014]
　The present inventors have made intensive studies to solve the above problems, as a viscosity modifier, in addition to the constituent unit derived from ricinoleic acid, furthermore, the specific co-comprising specific structural units in a specific ratio by employing polymers, it can solve the above problems, and have completed the present invention.
[0015]
　That is, the present invention relates to the following [1] to [16].
[0016]
　[1]
　following requirements (B1) satisfying ~ a (B3) copolymer
　(B): and (B1) constituting unit derived from ricinoleic acid (a),
　　　　　and the structural unit derived from an aliphatic dicarboxylic acid (b),
　　　　　a constituent unit derived from a diol having a carbon number of 2 ~ 10 (c)
including;
　(B2) the structural unit (a), when the sum of 100 mol% of (b) and (c), the structural unit content of 20 to 90 mol% of (a), content of 5 to 40 mol% of the structural unit (b), the content of the structural unit (c) is 5 to 40
　mol%; (B3) an intrinsic viscosity [ IV] is in the range of 0.1 ~ 2.0dl / g.
[0017]
　[2]
　base oil (A) and, wherein the copolymer according (B) in [1]
include, and the weight ratio of the base oil (A) and the copolymer (B) ((A mass / (weight of B)) is a lubricating oil composition is 60/40 to 99.5 / 0.5).
[0018]
　[3]
　The base oil (A) is a lubricating oil composition according to [2] is a vegetable oil and / or synthetic esters.
[0019]
　[4]
　the synthetic ester lubricating oil composition according to the a diester or polyolester [3].
[0020]
　[5]
　The synthetic ester, wherein an aliphatic diester or aliphatic polyol ester [3] or lubricating oil composition according to [4].
[0021]
　[6]
　In the requirement (B2), the molar ratio of the structural unit (b) and the structural unit (c) ((b) / (c)) is 0.9-1.1, the [2 the lubricating oil composition according to any one of to [5].
[0022]
　[7]
　In the requirement (B2), the structural unit (a) is 40 to 90 mol%, the [2] to the lubricating oil composition according to any one of [6].
[0023]
　[8]
　In the requirement (B3), an intrinsic viscosity [IV] is in the range of 0.3 ~ 1.5 dl / g, the [2] a lubricating oil composition according to any one of - [7].
[0024]
　[9]
　antioxidants, extreme pressure agents, rust inhibitors, metal deactivators, antiwear additives, defoamers, at least one additive selected from detergent-dispersant and the group consisting of pour point depressant ( wherein further comprising a C) [2] ~ lubricating oil composition according to any one of [8].
[0025]
　[10]
　The aliphatic dicarboxylic acid is sebacic acid, the [2] a lubricating oil composition according to any one of - [9].
[0026]
　[11]
　diols of the C 2 -C 10 is 1,4-butanediol, the [2] to the lubricating oil composition according to any one of [10].
[0027]
　[12]
　The [2] to [11] Gear oil consisting of the lubricating oil composition according to any one of.
[0028]
　[13]
　The [2] to [11] hydraulic oil consisting of the lubricating oil composition according to any one of.
[0029]
　[14]
　The [2] to [11] Engine oil consisting of the lubricating oil composition according to any one of.
[0030]
　[15]
　The [2] to [11] grease consisting lubricating oil composition according to any one of.
[0031]
　[16]
　The [2] to [11] machine oil consisting of the lubricating oil composition according to any one of.
Effect of the invention
[0032]
　According to the present invention, as a viscosity modifier in lubricating oil compositions, it is possible to provide the workability (handling ability, solubility) and excellent biodegradable copolymer. Further, by using the copolymer, shear stability, it is possible to provide a lubricating oil composition having both low-temperature fluidity, heat resistance (discoloration inhibition during heating) and sticky.
DESCRIPTION OF THE INVENTION
[0033]
　Hereinafter, the copolymers and lubricating oil compositions according to the present invention will be described in detail for each constituent element.
[0034]
　[Base Oil (A)]
　The lubricating oil composition according to the present invention comprises base oil (A). In the present invention, as the type of base oil (A), mention may be made of vegetable oils, synthetic esters, low molecular weight poly α- olefins, and the like. Among these vegetable oils, synthetic esters are preferred. In this case, the base oil (A) may be a vegetable oil may be a synthetic ester, or may be a combination of these.
[0035]
　Incidentally, the synthetic esters used as the base oil (A) is different from the later-described copolymer (B). That is, in the present invention, esters may be applicable to both the copolymer to be described later synthetic esters which can be used as the base oil (A) (B) is treated as corresponding to the copolymer (B) to be described later .
[0036]
　Here, preferred examples of the vegetable oil, rapeseed oil, soybean oil, castor oil, palm oil, sunflower oil, safflower oil, corn oil, meadowfoam oil, rice bran oil, olive oil, jojoba oil and the like, these among them, rapeseed oil, soybean oil, castor oil, palm oil is more preferable. Further, these plant oils singly or may be used in combination of two or more. These vegetable oils are excellent biodegradable.
[0037]
　On the other hand, preferred examples of the synthetic esters, diesters, polyol esters. When these are used as the base oil (A), preferably the lubricating oil composition obtained become available in a wide range of temperature conditions.
[0038]
　Diesters, of the polyol ester, as preferable examples of the diester, di-2-ethylhexyl sebacate, dioctyl adipate, dioctyl dodecanedioate, diisodecyl adipate, include aliphatic diesters such as dioctyl sebacate, a suitable polyol ester as an example, pentaerythritol tetraoleate, trimethylolpropane pelargonate, aliphatic polyol esters such as neopentyl polyol fatty acid esters. When these aliphatic diesters and aliphatic diesters employed as base oil (A), further, a wide range of temperature conditions from low temperature range (below room temperature) to a high temperature range (50 ° C. ~ 100 ° C.), the lubricating oil composition is preferable since it becomes available.
[0039]
　These synthetic esters, singly or may be used in combination of two or more.
[0040]
　Incidentally, as a base oil (A), and one or more types of vegetable oils may be used by mixing one or more kinds of synthetic esters.
[0041]
　Further, in order to obtain a lubricating oil composition having a proper lubrication, (according to ASTM 445 kinematic viscosity test method) kinematic viscosity at 40 ° C. of the base oil (A) is, 10 ~ 80 mm 2 to a / s preferably, 14 ~ 60 mm 2 and even more preferably from / s.
[0042]
　Further, in order to obtain a lubricating oil composition having a proper fluidity in a low temperature range (room temperature or below), that the pour point of the base oil (A) to (according to the measurement method of JIS K2269) to 0 ~ -50 ° C. It is preferred.
[0043]
　Copolymer (B)]
　The lubricating oil composition according to the present invention comprises a copolymer (B) as a viscosity modifier. In the present invention, copolymer (B) satisfying the following requirements (B1) ~ (B3).
[0044]
　Requirements (B1): a structural unit derived from ricinoleic acid and (a),
　　　　　　　　and the structural unit derived from an aliphatic dicarboxylic acid (b),
　　　　　　　　a constituent unit derived from a diol having a carbon number of 2 ~ 10 (c)
including .
[0045]
　[Constituent units derived from ricinoleic acid (a)]
　constitutional unit derived from ricinoleic acid in the present invention (a) (hereinafter, simply referred to as "structural unit (a)".) And the ricinoleic acid (12 - hydroxy -cis-9-octadecenoic acid) or a structural unit derived from ricinoleic acid derivatives. In the present invention, the copolymer (B) by including such structural units (a), the lubricating oil composition obtained has excellent storage stability and viscosity characteristics and can be expected high biodegradability.
[0046]
　Derivatives of ricinoleic acid, for example, condensation products of ricinoleic acid, ester (e.g. methyl ricinoleate) with ester or ricinoleic acid with alcohols of the ricinoleic acid and a carboxylic acid, reaction products of ricinoleic acid and an epoxy compound , ricinoleic acid was hydrogenated 12-hydroxystearic acid and condensates thereof, such as 12-hydroxystearic acid and a carboxylic acid or ester of an alcohol (e.g., 12-hydroxystearic acid methyl ester), the ricinoleic acid by the polymerization reaction various compounds give origin constituting unit (a).
[0047]
　In this specification, a monomer component corresponding to the structural unit (a), namely the derivatives of the ricinoleic acid and ricinoleic acid, may be referred to as "monomer component (a ')".
[0048]
　Thus, the derivative of ricinoleic acid, since it is also 12-hydroxystearic acid and esters thereof are encompassed structural unit in the present invention (a) is specifically represented by the following formula (1) or the following is a structural unit represented by the formula (2).
[0049]
[Formula 1]

　Here, the total proportion of the constituent unit derived from occupying the 12-hydroxystearic acid and ester derivatives thereof all the structural units (a), i.e., by the above formula to the total structural units (a) (2) the total proportion of the structural units represented by is not particularly limited, is represented by the sum of the structural units derived from ricinoleic acid (a) (i.e., the structural unit and the formula represented by the above formula (1) (2) the total) of the constituent units is 100 mol% that is any in the range of 0 to 100 mol%. However, in the present invention, since it is the easily obtained lubricating oil composition having high transparency and high cold flow tendency of building blocks derived from ricinoleic acid (a) is represented by the above formula (1) preferably includes a structural unit. The proportion In this sense, preferably from 0 to 80 mol%, more preferably 0 to 60 mol%. Said that in the preferred range, excellent in terms of dispersibility of fluidity at low temperatures and to the base oil (particularly a vegetable oil). However, lubricating oil compositions of the present invention, when subjected to the necessarily high transparency and does not require applications, when used in, for example, grease, etc., the ratio is not necessarily in the above preferable range, for example, constitutional unit derived from ricinoleic acid (a) is not excluded that consist only structural units represented by the above formula (2).
[0050]
　[Constituent units derived from an aliphatic dicarboxylic acid (b)]
　structural units derived from an aliphatic dicarboxylic acid (b) (hereinafter, simply referred to as "structural unit (b)".) Is an aliphatic dicarboxylic acid or derived from an aliphatic dicarboxylic acid ester. Structural unit in the present invention (b), specifically, formally, is a structural unit having a structure obtained by removing -OH from two carboxyl groups contained in the aliphatic dicarboxylic acid.
[0051]
　It aliphatic dicarboxylic acids leading to structural unit (b) is an aliphatic, preferably in order not to lower the solubility biodegradable base oil of the copolymer obtained.
[0052]
　Examples of the aliphatic dicarboxylic acid, ester polymerization functional group having reactivity with the reaction system to be carried out, for example, a hydroxyl group, a not particularly limited as long as no besides, may be a combination of two or more even alone. Specifically, malonic acid (3 carbon atoms), dimethyl malonate (5 carbon atoms), succinic acid (4 carbon atoms), glutaric acid (5 carbon atoms), adipic acid (6 carbon atoms) , 2-methyl adipic acid (7 carbon atoms), trimethyl adipic acid (number of carbon atoms 9), pimelic acid (carbon atoms 7), 2,2-dimethyl glutaric acid (7 carbon atoms), 3,3 diethyl succinate (carbon atoms 8), suberic acid (8 carbon atoms), azelaic acid (carbon atoms 9), and the like sebacic acid (10 carbon atoms). On the other hand, as the aliphatic dicarboxylic acid ester, various esters of the aliphatic dicarboxylic acid.
[0053]
　Among them, preferred are aliphatic dicarboxylic acids having 6 to 12 carbon atoms, particularly preferably sebacic acid.
[0054]
　In the present specification, sometimes monomer components corresponding to the structural unit (b), i.e. the aliphatic dicarboxylic acids and aliphatic dicarboxylic acid ester, referred to as "aliphatic dicarboxylic acid component (b ')" .
[0055]
　[Constituent units derived from a diol having a carbon number of 2 to 10 (c)]
　the constituent unit derived from a diol having 2 to 10 carbon atoms (c) (hereinafter, simply referred to as "structural unit (c)" .), specifically, formally, it is a structural unit having a structure obtained by removing -H two hydroxyl groups contained in the diol having 2 to 10 carbon atoms. Direct constitutive units (c), the diol having 2 to 10 carbon atoms, may be a combination of two or more types may be alone, in particular the compounds below.
[0056]
　As diols having 2 to 10 carbon atoms, aliphatic diols having 2 to 10 carbon atoms. Examples of such aliphatic diols, 1,2-ethanediol (ethylene glycol: 2 carbon atoms), 1,3-propanediol (trimethylene glycol: carbon atoms 3), 1,2-propanediol ( propylene glycol: carbon atoms 3), 1,4-butanediol (tetramethylene glycol: 4 carbon atoms), 2,2-dimethyl-1,3-diol (neopentyl glycol: carbon atoms 5), 1 , 6- hexanediol (hexamethylene glycol: 6 carbon atoms), 1,8-octanediol (octamethylene glycol: carbon atoms 8), 1,9 (nonamethylene glycol: -C 9) including and the like.
[0057]
　The side-chain alkyl group containing glycol Among such aliphatic diol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-hexyl-1,3-propanediol, 2-hexyl-1,6-propanediol, neopentyl glycol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl -2-n - butyl-1,3-propanediol, 1,3-nonanediol, 2-methyl-1,8-octanediol, and the like.
[0058]
　Particularly preferred among the above diol is 1,4-butanediol.
[0059]
　In this specification, a monomer component corresponding to the structural unit (c), i.e., the diol of the 2 to 10 carbon atoms, may be referred to as "diol component (c ')."
[0060]
　Or as a copolymer (B) used in the present invention, in addition to the above structural units (a), which also include the above-described structural units (b) and (c). By thus copolymer (B) is also including the structural units (b) and (c), heat resistance and handling properties in the lubricating oil composition obtained, more precisely, the following Examples below in as shown, excellent adhesiveness and heat resistance. Reason for such an effect is obtained will be described later in later "feature of the copolymer (B)".
[0061]
　[Other structural units]
　copolymer (B) used in the present invention, which is preferably composed only by the above structural units (a) ~ (c), as long as it does not inhibit the effects of the present invention, the of the structural unit (a) ~ structural unit corresponds to none of (c) (hereinafter, "other structural unit") may further comprise a. Other structural units, flanges carboxylic acids such as 2,5-furan dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2 - methyl terephthalic acid, aromatic dicarboxylic acids such as naphthalene dicarboxylic acid, such as a structural unit derived from a variety of dicarboxylic acids and carboxylic acid esters which does not correspond to the aliphatic dicarboxylic acid component (b '), the number 11 or more carbon atoms constituent units derived from an aliphatic diol, structural units derived from aromatic diol, trimethylol ethane, polyhydric alcohols 3 or more valences such as glycerin, butane tricarboxylic acid, tri- or higher polycarboxylic of trimellitic acid, etc. acid, and oxydicarboxylic acids such as 4-hydroxy-phthalic acid.
[0062]
　In this specification, a monomer component corresponding to the "other structural unit", that is, various dicarboxylic acids or carboxylic acid ester does not correspond to the above-mentioned the aliphatic dicarboxylic acid component (b '), the number of carbon atoms 11 or more aliphatic diols, aromatic diols, trihydric or higher polyhydric alcohols, trivalent or higher polyvalent carboxylic acid and oxy dicarboxylic acids such as may be referred to as "other monomer component".
[0063]
　Requirements (B2): the structural units (a), (b) and when the total of 100 mol% of (c), content of 20 to 90 mol% of the structural units (a), the structural units (b) content of between 5 to 40 mol% of a content of the structural unit (c) 5 to 40 mol%.
[0064]
　Although the lower limit of the content of the thus the structural units (a) is 20 mol%, more preferably 30 mol%, more preferably 40 mol%, particularly preferably 50 mol%. It the content of the structural units (a) is 20 mol% or more is preferable in terms of imparting moderate stickiness properties. If it is 30 mol% or more, and the viscosity properties of the resulting composition, more preferred from the viewpoint of improving the turbidity of the storage stability i.e. the base oil (haze). Storage stability is 40 mol% or more are especially preferred. Further, preferably shear stability. On the other hand, the upper limit of the content of the constituent units (a) is a 90 mol%, more preferably 85 mol%. The content of the structural units (a) is preferred in terms of heat resistance and stickiness of the composition obtained is not more than 90 mol%. Given these, the content of the structural units (a) is preferably 40 to 90 mol%, more preferably 45 to 85 mol%.
[0065]
　Further, it is preferable that the molar ratio of the structural units (b) and the structural unit (c) ((b) / (c)) is 0.9 to 1.1.
[0066]
　In the manufacturing method described later, it is adjustable in the range by changing the ratio of introducing ricinoleic acid or ricinoleic acid derivative, a diol of an aliphatic dicarboxylic acid and 2 to 10 carbon atoms to the polymerization system.
[0067]
　Copolymer (B) according to the present invention, which is preferably composed only of the structural units (a) ~ (c) as described above, as long as it does not inhibit the effect of the invention, contain other structural units it may be Idei. If copolymer (B) comprises additional structural units, the content of other constituent units in the copolymer (B) is the sum of the structural units (a) ~ (c) and another structural unit 100 as mol%, preferably 20 mol% or less, more preferably 10 mol% or less, particularly preferably not more than 5 mol%.
[0068]
　Incidentally, the content of the structural units in the copolymer (B) (a) ~ (c) and "other structural unit" can be determined by a suitable technique such as NMR.
[0069]
　Requirements (B3): The intrinsic viscosity [IV] is in the range of 0.1 ~ 2.0dl / g. Preferably 0.1 ~ 1.5dl / g, more preferably 0.2 ~ 1.5dl / g, more preferably 0.2 ~ 1.0dl / g, especially preferably 0.2 ~ 0.6 dl / g it is. Excellent workability of the copolymer by the above range, excellent shear stability other various physical properties of the resulting composition.
[0070]
　Measurement conditions of intrinsic viscosity [IV] are as described in the Examples section. By using the copolymer (B) having an intrinsic viscosity [IV] of the above range, the lubricating oil composition obtained excellent thickening, it is possible to impart viscosity index improving effect. Further, the base oil (A) is the case of vegetable oil, it is possible to impart good low-temperature storage stability to the lubricating oil composition obtained. The intrinsic viscosity [IV] can be adjusted to the above range by adjusting the molecular weight of the copolymer (B).
[0071]
　Further, the copolymer (B) used in the present invention, if desired, the copolymer (B) a copolymer containing a structural unit represented by the above formula (1) as the structural units (a) of ( B0) may be made by performing processing such as hydrogenating.
[0072]
　Features of the copolymer (B)]
　The copolymer of the present invention (B) is secondary hydroxyl (12-position hydroxyl group) less ester bond derived from compared to the homopolymer of ricinoleic acid derivatives, adjacent ester wherein the length between groups (the length in the carbon of the carbon chain) comprises a relatively short structure. Since this means that less thermally unstable linkages in the copolymer (B), is believed to contribute to heat stability. It ester group density is high, tends to take a compact structure by intermolecular interactions, it is believed to contribute to workability (handleability and solubility).
[0073]
　Further, the copolymer (B) of the present invention, compared to the homopolymer of ricinoleic acid derivatives, can proceed more stably ester polymerization reaction since the primary hydroxyl group is often a monomer component, heavy dehydration in the polymer is suppressed, is considered effective for excellent heat stability by double bond amount is suppressed copolymer obtained is obtained.
[0074]
　Further, the copolymer (B) of the present invention, compared to the homopolymer of ricinoleic acid derivatives, in the long ratio of ricinoleic acid derivatives having a side chain at that relatively low, resulting lubricating oil composition it is considered that excellent shear stability.
[0075]
　[Copolymer Production method of (B)]
　The copolymer (B), the above structural units (a), a compound leading to (b) and (c), i.e., the monomer component (a ') , obtained by performing the ester polymerization reaction to the aliphatic dicarboxylic acid component (b ') and the diol component (c'). That is, a ricinoleic acid or ricinoleic acid derivatives described above in the section "structural unit derived from ricinoleic acid (a)", or aliphatic dicarboxylic acids described above in "structural unit (b) derived from an aliphatic dicarboxylic acid" above aliphatic dicarboxylic acid esters can be obtained by mutually ester polymerization reaction with a diol of the carbon atoms 2 to 10 described above in the section "structural unit derived from a diol having 2 to 10 carbon atoms (c)". The ester polymerization reaction, various dicarboxylic acids mentioned above in the section "other structural unit" carboxylic acid ester, carbon atoms 11 or more aliphatic diols, aromatic diols, trihydric or higher polyhydric alcohols, trivalent or higher polycarboxylic acids, when in the presence of such oxy-dicarboxylic acid, "other structural units"
can be obtained copolymer also containing a (B).
[0076]
　The production method can be applied conventionally directly known methods esterification method, an ester exchange method or the like.
[0077]
　In the direct esterification method, the monomer component (a '), the aliphatic dicarboxylic acid component (b'), the diol component (c ') and optional the "other monomer component" a conventional manner by directly polycondensation, it is possible to obtain a copolymer. For example,
　　'a, the monomer component (a)
　　a dicarboxylic acid component (the aliphatic dicarboxylic acid component (b'), and, various dicarboxylic acids mentioned above in the section "other structural unit") and,
　　diol (the diol component (c '), and said section various diols) and described above in "other structural units"
was heated at pressure, while removing generated condensation water from the reaction system of low molecular weight condensate after distilled off the titanium compound, germanium compound, outside the system diol by reducing the pressure in the reaction system in the presence of a polycondensation catalyst such as antimony compounds. Thus, it is possible to produce a high molecular weight polyester resin. In this example, the mentioned case of reacting a dicarboxylic acid component and a diol and the monomer component (a '), the trihydric or higher polyhydric alcohols and the "other monomer component" / or it can be a trivalent or higher polyvalent carboxylic acid is carried out in the same manner also in the case of coexistence.
[0078]
　Further, in the transesterification method may employ a corresponding dialkyl ester of a dicarboxylic acid as the starting material. In this case, the aliphatic dicarboxylic acid component (b ') as adopts the corresponding dialkyl ester, the monomer component (a'), the diol component (c ') and optional the "other single together mer component ", by directly polycondensing by a conventional method, it is possible to obtain a copolymer. At this time, for the various dicarboxylic acids mentioned above in the monomer component (a ') and / or the section "other structural unit" may be used in the form of corresponding alkyl esters. For example,
　　'a, the monomer component (a)
　　a dicarboxylic acid (the aliphatic dicarboxylic acid component (b'), and, various dicarboxylic acids mentioned above in the section "other structural unit") and dialkyl esters of
　　diols (the diol component (c '), and said sections various diols described above in "other structural units") and
heated at atmospheric pressure, while removing the product alkyl alcohol from the reaction system of low molecular weight condensate after a, evaporated titanium compound, a germanium compound, a diol and a reduced pressure of the reaction system in the presence of a polycondensation catalyst such as antimony compounds from the system. Thus, it is possible to produce a high molecular weight polyester resin. In this example, the mentioned case of reacting a dialkyl ester and a diol of a dicarboxylic acid as the monomer component (a '), 3 or more valences alcohol as the "other monomer component" and / or trivalent or higher polyvalent carboxylic acid can be carried out similarly also in the case of coexistence.
[0079]
　Although reactions are esterification reaction in the direct esterification method and the transesterification method in the absence of a catalyst to proceed, it is preferable to use a polycondensation catalyst as exemplified above.
[0080]
　Direct esterification process, in any of the manufacturing process by an ester exchange method, in order to keep the reaction system in a uniform liquid state while heating the reaction system so as not to fall below the melting point of the oligomer and the polyester reaction temperature to produce reaction is made proceed. If it is necessary to increase further the molecular weight (weight average molecular weight), it is also possible to increase the molecular weight subjected to solid phase polymerization in the copolymerization polyester resin obtained by melt polymerization.
[0081]
　Copolymer (B) of the present invention can be prepared by ester polymerization reaction by lipase. In this method, the monomer component (a '), the aliphatic dicarboxylic acid component (b'), the "other monomer component" of the diol component (c ') and optionally in the presence of lipase by condensation polymerization, it is possible to obtain a copolymer. The lipase, Burkholderia cepacia from immobilized lipase (e.g., manufactured by Wako Chemical Co., Ltd., Lipase PS-C Amano II (trade name), PS-D Amano I (trade name)) are preferable, in this case, high temperature But for lipase hardly inactivated, the reaction temperature can be raised up to 90 ° C.. As the reaction conditions, in bulk conditions, it is preferable that the batch method according stirred reactor. As the reaction time, the catalyst concentration may vary with conditions such as the polymerization temperature is usually 4-7 days.
[0082]
　Further, ester polymerization reaction is a reversible reaction, in order to advance the efficient polymerization reaction, it is preferable to sequentially remove the produced alcohol or water. Specifically, the pressure conditions in the reaction system or maintained in a reduced pressure state, synthetic zeolite (e.g., molecular sieves 4A) or to implement synthesis reaction after having established a hygroscopic agent such as a non-contact in the reaction system and the like. By carrying out the polymerization reaction under these conditions, it is possible to proceed simply and easily polymerization reaction, the copolymer (B) can efficiently be synthesized in good.
[0083]
　In the present invention, the monomer component in each ester polymerization reaction (a '), the aliphatic dicarboxylic acid component (b'), said diol component (c ') and option of "other monomer component charged amount ratio of "the copolymer (B) of the structural units to be achieved (a), the can be appropriately adjusted depending on the content of (b), (c) and" other structural unit " .
[0084]
　Copolymers obtained by these such ester polymerization reaction may be adopted as the copolymer (B) as it forms, further carrying out the hydrogenation reaction using a conventionally known appropriate method Accordingly, it may be subjected to hydrogen addition per part or all of the double bonds contained in the structural units (a). For example, first, the ester polymerization reaction to prepare the copolymer a copolymer containing a structural unit represented by the above formula (1) as the structural units (a) of (B) (B0), then the copolymer (B0) may be subjected to a treatment such as partially or fully hydrogenated and may be employed such products obtained by hydrogenation as a copolymer (B).
[0085]
　Lubricating Oil Composition
　In the lubricating oil composition of the present invention, the mass ratio of the base oil (A) and the copolymer (B) ((mass of the mass / (B) of the A)) is 60 / is 40 to 99.5 / 0.5, preferably 75 / 25-99 / 1, more preferably from 80 / 20-1 97/3. In such a range, good compatibility between The inclusion of the base oil (A) and the copolymer (B) in the lubricating oil composition, the base oil (A) and the copolymer (B) together is obtained, the thickening effect is imparted to the lubricating oil composition. Further, even at room temperature conditions, for lubricating oil compositions can exhibit the proper viscosity index, it is excellent flowability. Furthermore, when the base oil (A) is a vegetable oil, it is possible to improve the low-temperature storage stability of the lubricating oil composition.
[0086]
　Further, the lubricating oil composition, medium temperature range since it can impart proper lubrication performance in (room temperature ~ 50 ° C.), (conforming to ASTM D445) kinematic viscosity at 40 ° C. of the lubricating oil composition according to the present invention, 50 ~ 700 mm 2 preferably to / s, 80 ~ 600 mm 2 and even more preferably from / s.
[0087]
　Further, the lubricating oil composition, since it can impart proper lubrication performance in a high temperature range (50 ℃ ~ 100 ℃), ( conforming to ASTM D445) a kinematic viscosity at 100 ° C. of the lubricating oil composition according to the present invention, 10 ~ 100 mm 2 preferably to / s, 15 ~ 70 mm 2 and even more preferably from / s.
[0088]
　Further, it becomes to be used in a wide temperature range lubricating oil composition, because it can maintain the proper lubrication at each temperature, (according to ASTM D2270) viscosity index of the lubricating oil composition according to the present invention, 180 preferably to to 250, more preferably 200 to 250.
[0089]
　The lubricating oil composition of the present invention is biodegradable can be expected high from the composition. Further, when the lubricating oil composition is scattered in nature (leakage), since it is desirable to be rapidly degraded in the natural environment (biodegradation), modification of the lubricating oil composition of the present invention MITI Test Method preferably biodegradation rate based on the "OECD301C" is 40% or more, more preferably 60% or more.
[0090]
　Additives (C)]
　The lubricating oil composition according to the present invention, in addition to the base oil (A) and copolymer (B), oxidation stability, rust resistance, extreme pressure, anti-foaming properties such as improvement depending on the purpose of, preferably contains an additive (C).
[0091]
　Examples of such additives (C), antioxidants, extreme pressure agents, rust inhibitors, metal deactivators, antiwear additives, defoamers, from the group consisting of detergent dispersant and pour point depressant it is preferably at least one selected.
[0092]
　The total amount of additive (C) may be appropriately added in amounts not detrimental to the objects of the present invention, the lubricating oil composition with respect to 100 mass%, 0.05 to 25 mass% it is preferable.
[0093]
　[Antioxidant]
　The antioxidant used in lubricating oil compositions of the present invention, known antioxidants may be used, specifically, di (alkylphenyl) amine (the alkyl group having a carbon number 4 to 20 ), phenyl -α- naphthylamine, alkyldiphenylamine (the alkyl group of 4 to 20 carbon atoms), N- nitrosodiphenylamine, phenothiazine, N, N'-dinaphthyl -p- phenylenediamine, acridine, N- methyl phenothiazine, N- ethyl phenothiazine, dipyridylamine, diphenylamine, phenolamine, 2,6-di -t- butyl--α- dimethylamino para amine antioxidants such as cresol, 2,6-di -t- Buchiruparakurezo - le, 4,4 ' - methylenebis (2,6-di -t- butylphenol - Le), 2,6-di -t- butyl -4-N N- dimethylaminomethyl phenol, 2,6-di -t- butylphenol - le, phenol such as dioctyl diphenylamine - Le antioxidant, also iron octoate, ferrocene, iron naphthoate of the organic iron salts, cerium naphthoate, Seriumutorue - organic cerium salts such bets, organometallic compound based antioxidants such as organic zirconium salts such as zirconium octoate and the like. Also, antioxidants may be used alone, it may be used in combination of two or more.
[0094]
　[Extreme pressure agent]
　As the extreme pressure agent for use in the lubricating oil composition of the present invention, although known extreme pressure additives can be used, specifically, chlorinated paraffin, chlorinated diphenyl, and the like chlorinated fatty chlorine compounds; sulfurized fatty acids, sulfurized fatty esters, animal oils sulfurized vegetable oil sulfide, dibenzyl disulfide, synthetic polysulfide, sulfur and alkyl thio amine salts or alkali metal salts of acid and amine salts or alkali metal salts of alkyl thioglycolic acid, system compound; phosphoric acid esters, acidic phosphoric acid esters, amine salts of acidic phosphoric acid esters, and phosphorus-based compounds such as chlorinated phosphoric esters and phosphorous acid esters, zinc dialkyldithiophosphates compound or diallyl dithiophosphate, zinc compounds, organic molybdenum compounds, metal soaps such as lead naphthenate, organic C acid esters and their metal salts or amine salts, organic phosphonic acids and their metal salts or amine salts.
[0095]
　Extreme pressure agents, in the lubricating oil compositions of the present invention can be added one or more, the combination of extreme pressure additives used in the case of adding two or more kinds, the characteristics of the lubricating oil composition obtained is desired as may have, it can be arbitrarily combined.
[0096]
　The content of extreme pressure agent in the lubricating oil composition of the base oil (A) 100 parts by mass of, it is preferably 0.5 to 10 parts by weight, 2 to 8 parts by mass A further preferred.
[0097]
　[Rust]
　Examples of the rust inhibitor to be used in the lubricating oil composition of the present invention, for example, petroleum sulfonates, alkylbenzene sulfonates, dinonyl naphthalene sulfonates, alkenyl succinic acid esters, and polyhydric alcohol esters.
[0098]
　[Metal deactivator]
　Examples of the metal deactivator used in the lubricating oil compositions of the present invention, mention may be made of benzotriazole and derivatives thereof, and thiazole compounds.
[0099]
　[Antiwear additives]
　Examples of anti-wear additives, phosphorus-based compounds, organic molybdenum compounds, fatty acid ester compounds or aliphatic amine compounds.
[0100]
　The anti-wear additives of the phosphorus-based compounds, such as alkyl zinc dithiophosphate, phosphoric acid, phosphorous acid, phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid triesters, phosphite monoesters, phosphorous phosphoric acid diesters, triesters of phosphorous acid, (sub) salts of phosphoric acid esters, and thiophosphoric acid or thiophosphorous acids or their esters, and mixtures thereof. Among these, alkyl zinc dithiophosphate is preferably used, usually 2 to 30 carbon atoms, preferably containing a hydrocarbon group of 3 to 20. The hydrocarbon group of 2 to 30 carbon atoms, e.g., alkyl group, cycloalkyl group, alkylcycloalkyl group, an alkenyl group, an aryl group, an alkylaryl group, and can be exemplified arylalkyl group.
[0101]
　Examples of the organic molybdenum compound antiwear additives, such as molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum acid amine salts. In particular, a molybdenum dithiocarbamate is preferred.
[0102]
　[Antifoaming]
　As the defoaming agents used in the lubricating oil composition of the present invention, although known defoaming agents can be used, for example, dimethyl siloxane, silicon antifoaming agent silica gel dispersion, etc .; alcohols, esters such as anti-foaming agents, and the like.
[0103]
　[Detergent dispersant]
　The detergent-dispersant employed in the lubricating oil composition of the present invention, known detergent-dispersant can be used, for example, calcium sulfonate, magnesium sulfonate, and barium sulfonate metal sulfonate or thiophosphonates, phenates, salicylates, succinimides, benzyl amine, and the like succinic acid ester.
[0104]
　[Pour point depressants]
　The pour point depressants, alkylated naphthalene, (co) polymers of alkyl methacrylate, (co) polymers of alkyl acrylate, copolymers of alkyl fumarate and vinyl acetate, alpha- olefin polymers, and a copolymer of α- olefin and styrene. In particular, the alkyl methacrylate (co) polymers, and the like of the alkyl acrylate (co) polymer.
[0105]
　[Method of making a lubricating oil composition]
　The lubricating oil composition of the present invention, the base oil (A) and a predetermined copolymer (B), the additive (C) or the like are mixed and kneaded at a predetermined ratio by the need obtained Te.
[0106]
　Added Here, when the base oil (A), copolymer (B), depending on need mixing and kneading the additive (C) or the like, these components simultaneously or in any order, the mixing and kneading apparatus it may be.
[0107]
　Further, as the mixing and kneading means, tank blending method, a known mixing and kneading apparatus such as automatic blender system can be used.
[0108]
　Furthermore, the mixing and kneading may be carried out at room temperature, in order to improve the uniformity of each component in the lubricating oil composition, the components, while heating or after heating to 60 ~ 80 ° C. mixture - it is preferable that the kneading.
[0109]
　[Use of the lubricating oil composition]
　The lubricating oil composition according to the present invention has a good viscosity characteristics and friction characteristics, in order to have excellent biodegradability, very useful as a lubricating oil composition of each application it is.
[0110]
　Specific applications, for example, gear oil, hydraulic oil, engine oil, grease, machining oil, sliding surface oil, electrical insulating oil, turbine oil, gear oil, air compressor oil, compressor oil, vacuum pump oil, bearing oil, thermal oil, mist oil, refrigerator oil, rock drill oil are preferred. Here, as the engine oil, two-cycle engine oil, gasoline engine oils, such as diesel engine oils. Moreover, as the machining oil, for example, cutting oil, grinding oil, punching oil, drawing oil, press oil, drawing oil, rolling oil, forging oil.
Example
[0111]
　Will now be described in further detail by showing Examples The present invention, the invention is not intended to be limited by these.
[0112]
　[Base Oil]
　The properties of the following base oils used in the examples and comparative examples in Table 1 below.
[0113]
　A-1: rapeseed oil: MP Biomedical, Inc.
　A-2: DIDA (diisodecyl adipate): Daihachi Chemical Industry Co., Ltd.
　A-3: H-334R (neopentyl polyol fatty acid ester): manufactured by NOF Corporation
[0114]
[Table 1]

　Copolymer Production and Evaluation Method]
　shown copolymer properties measurement conditions and production conditions, and the evaluation criteria of the properties of the lubricating oil composition as follows.
[0115]
　[(Co) Measurement of the content of each constituent unit constituting the polymer]
　content obtained in the manufacturing example below (co) each of the structural units constituting the polymer was determined by the following procedure.
[0116]
　Using JEOL Ltd. ECA500 type nuclear magnetic resonance device, the solvent used was deuterated chloroform. Sample concentration 35 mg / 0.5 mL, the measured temperature was 50 ° C.. Observation nucleus IH (500 MHz), the sequence is single pulse, pulse width 6.3μ sec (45 ° pulse), repetition time 8.5 sec, the integration number 394 times, the hydrogen signal tetramethylsilane chemical shift It was measured as a reference value. Each peak was assigned by a conventional method.
[0117]
　[Intrinsic viscosity measurements (IV)]
　The intrinsic viscosity (IV: Intrinsic Viscosity), a sample (polyester resin) and 0.5 g 1,1,2,2-tetrachloroethane / phenol mixed solution (50 wt% / 50 wt %) was dissolved with 100 ml, in the mixed solution was cooled at 25 ° C. water after 40 minutes heated and dissolved at 135 ° C., measured solution viscosity at 25 ° C. using an Ubbelohde viscometer, is calculated .
[0118]
　The intrinsic viscosity is a value calculated by the following formula.
[0119]
　[eta] = eta SP / [C (1 + Keiita SP )]
　　[eta]: intrinsic viscosity (dl / g)
　　eta SP : specific viscosity
　　C: sample concentration (g / dl)
　　k: constant (solution concentration different samples the specific viscosity of (three or more) were measured, the solution concentration on the horizontal axis and the vertical axis eta SP slope obtained by plotting / C)
　, where specific viscosity eta SP was determined according to the following formula.
[0120]
　eta SP = (t-t0) / t0
　　t: falling seconds of the sample solution (in
　　seconds) t0: falling seconds of the solvent (s)
　[melting point (Tm), glass transition temperature (Tg) of]
　the copolymer (B) melting point (Tm) is a differential scanning calorimeter as a measuring device was measured using a (DSC220C type, Seiko Instruments Co., Ltd.). Specifically, it sealed copolymer of about 5mg to (B) for measurement in an aluminum pan and heated to 0.99 ° C. at 10 ° C. / min from room temperature. At 0.99 ° C. and held for 5 minutes, then cooled to -100 ° C. at 10 ° C. / min. After standing 5 minutes at -100 ° C., heating was performed a second time to 0.99 ° C. at 10 ° C. / min. The second time the peak temperature in heating (℃) as the melting point of the copolymer (Tm), was the displacement points corresponding to the glass transition and glass transition temperature (Tg).
[0121]
　[Workability (handling ability)]
　was placed in a container (co) polymer, it was evaluated based on the following criteria operability for transferred to a beaker containing the base oil.
[0122]
　　◎: 23 can be taken out by tilting the container at ℃.
[0123]
　　○: 23 can be taken out using a spatula at ° C..
[0124]
　　△: a removable and portable raised to 50 ° C..
[0125]
　[Workability (solubility)]
　after turning on (co) polymer base oil, stirred for 5 minutes at 60 ° C., it was evaluated based on the following criteria by visual observation.
[0126]
　　◎: have become completely uniform
　　○: 8% or more is in uniform
　　△: about half is in uniform
　[biodegradable]
　modified MITI test method conforms to the "OECD301C", the biodegradation rate It was measured. Incidentally, it has been Eco Mark Certification Criteria revised in July 1998, that the above biodegradation rate is 60% or more is required.
[0127]
　[Example 1-1] (Copolymer Production of B-1)
　40.0 parts by weight ricinoleic acid, 5.8 parts by mass of sebacic acid, 5.2 parts by weight of 1,4-butanediol over 30 minutes, the temperature was raised from room temperature to 210 ° C.. After reaching to 210 ° C., 0.20 parts by mass of titanium tetrabutoxide were added 0.03 parts by weight of 20 wt% aqueous solution of tetraethylammonium hydroxide, and held for 5 hours as it 210 ° C., the esterification reaction was carried out.
[0128]
　After completion of the esterification reaction, addition 1.36 parts by mass of titanium tetrabutoxide as the polymerization catalyst, the pressure was reduced while raising the temperature to over 60 minutes 230 ° C. to 0.133 kPa (1 Torr), it was carried out polycondensation reaction. The polycondensation reaction was conducted while stirring the reaction mixture. Here, as the polycondensation reaction proceeds, stirring torque required for stirring of the reaction mixture gradually increases. Exit polycondensation reaction when the stirring torque to a predetermined range is reached, by extracting polyester from the reaction vessel within 10 minutes.
[0129]
　[Example 1-2] (Copolymer production of B-2)
　40.0 parts by weight ricinoleic acid, 10.2 parts by mass of adipic acid, 9.7 parts by weight of 1,4-butanediol over 30 minutes, the temperature was raised from room temperature to 210 ° C.. Thereafter, to obtain a polyester in the same manner as in Example 1-1.
[0130]
　[Example 1-3] (Copolymer Production of B-3)
　40.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, over 30 minutes 9.7 parts by weight of 1,4-butanediol, the temperature was raised from room temperature to 210 ° C.. Thereafter, to obtain a polyester in the same manner as in Example 1-1.
[0131]
　[Example 1-4] (Copolymer production of B-4)
　20.0 parts by weight ricinoleic acid, 19.6 parts by weight of 12-hydroxystearic acid, 13.6 parts by mass of sebacic acid, 1,4-butanediol 9.7 parts by weight over 30 minutes, the temperature was raised from room temperature to 210 ° C.. Thereafter, to obtain a polyester in the same manner as in Example 1-1.
[0132]
　[Example 1-5] (Copolymer production of B-5)
　30.5 parts by weight ricinoleic acid, 20.6 parts by mass of sebacic acid, over 30 minutes 13.3 parts by weight of 1,4-butanediol, the temperature was raised from room temperature to 210 ° C.. Thereafter, to obtain a polyester in the same manner as in Example 1-3.
[0133]
　[Example 1-6 to Example 1-9] (Production of Copolymer B-6 ~ B-9)
　except that stirring torque to the extent each predetermined finishes polycondensation reaction when it reaches Example 1-3 to obtain a polyester in the same manner as. That is, Examples 1-6 to 1-9, per polycondensation reaction was carried out in Example 1-3, an embodiment went changing the size of the agitation torque with reference to terminate the reaction, degree of polymerization corresponding to example went changed.
[0134]
　[Example 1-10] (Copolymer production of
　B-10) 39.2 parts by weight of 12-hydroxystearic acid, 13.6 parts by mass of sebacic acid, 9.7 parts by mass of 30 minutes 1,4-butanediol over, the temperature was raised from room temperature to 210 ° C.. Thereafter, to obtain a polyester in the same manner as in Example 1-1.
[0135]
　[Comparative Example 1-1] (Production of ricinoleic acid homopolymer P-1)
　over a period of 30 minutes 60.0 parts by weight ricinoleic acid, the temperature was raised from room temperature to 210 ° C.. Thereafter, to obtain a polyester in the same manner as in Example 1.
[0136]
　[Comparative Example 1-2] (Preparation of adipic acid-1,4-butanediol copolymer P-2)
　30.0 parts by mass of adipic acid, 29.2 parts by weight of 1,4-butanediol over 30 minutes It was heated from room temperature to 210 ° C.. Thereafter, to obtain a polyester in the same manner as in Example 1.
[0137]
　The composition and physical properties of the resulting (co) polymer in the form of polyester shown in Table 2-1 and Table 2-2 in the Production Examples. Here, in Table 2-1 and Table 2-2, compound names shown in the column of the respective structural units represents a compound that is subjected to the formation of the structural unit. Taking copolymer (B-1) as an example, Table 2-1, the copolymer (B-1) is a 70 mol% of structural units derived from ricinoleic acid as a structural unit (a), and 15 mol% of structural units derived from sebacic acid as a structural unit (b), indicates that the constituent units derived from 1,4-butanediol as a structural unit (c) and a 15 mole% .
[0138]
　From Table 2-1 and Table 2-2, the copolymer of Example it can be seen that the excellent biodegradability none. Also, compared to Comparative Examples 1-1 ricinoleate homopolymer, has excellent workability to the size of the intrinsic viscosity [IV], to have excellent balance between workability and intrinsic viscosity [IV] It is seen.
[0139]
[table 2-1]

[0140]
[Table 2-2]

　[Evaluation method of lubricating oil composition]
　the lubricating oil composition (i) storage stability, (ii) viscosity characteristics (kinematic viscosity), (iii) viscosity characteristics (viscosity index), (iv) handling properties, and (v) heat resistance evaluation method shown.
[0141]
　(I) storage stability
　put lubricating oil composition 10g obtained in Examples and Comparative Examples screw-cap bottle 20 ml, and heated at 50 ° C. 30 minutes, allowed to stand to room temperature, 25 ° C., a temperature of 0 ℃ compatibility (flowability, crystallization) as storage stability under the conditions was evaluated based on the following criteria.
[0142]
　　○: The components of the lubricating oil composition, are uniformly dispersed, not separated.
[0143]
　　△: The components of the lubricating oil composition, but not separated, fine particles are seen to slightly crystallized.
[0144]
　　×: The components of the lubricating oil composition, as well as separation, crystallization coagulated microparticles are seen.
[0145]
　(Ii) viscosity characteristics (kinematic viscosity)
　kinematic viscosity: Based on ASTM D445, were determined kinematic viscosity of 100 ° C..
[0146]
　(Iii) viscosity characteristics (viscosity index)
　VI: calculated viscosity index based on ASTM D2270.
[0147]
　(Iv) shear stability (viscosity decreasing rate)
　Japanese Automotive Standards Organization (JASO: Japanese Automotive Standards Organization) ultrasonic shear stability test method specified in (JASO M347-95) on the basis of ultrasound for 1 h irradiation and to evaluate reduced rates of 40 ° C. kinematic viscosity before and after irradiation (%) of.
[0148]
Shear stability is a copolymer component in the lubricating oil is subjected to shear by the metal sliding portion, which is a measure of kinematic viscosity loss due to molecular chain cutting.
[0149]
　(V) low temperature fluidity (-10 ° C., -40 ℃
　viscosity) conforming to ASTM D2983, was measured -40 ℃ viscosity by Brookfield viscometer at -10 ° C. and -40 ℃.
[0150]
　(Vi) adhesive (stringing, adhesion)
　the adhesive of the lubricating oil were evaluated as follows.
[0151]
　Stringing is at room temperature, sandwiching a drop of sample between the thumb and forefinger, it was observed and evaluated the presence or absence of stringiness upon or against or release the both fingers. The adhesive strength, immersing a metal rod with a spiral groove attached to stirrer in the sample at room temperature, the sample is from a pull up state (liquid surface along the groove of the metal bar when rotating at 300rpm height / mm) were observed and evaluated.
[0152]
　On top of that, the stringing and adhesion comprehensively evaluate the tackiness of the lubricating oil on the basis of the determination of the evaluation results was performed by scoring the following.
[0153]
　　　Rating of 5; have sufficient stringing, exhibit high adhesive strength (more than 5mm)
　　　score 4; has stringing, exhibit high adhesive strength (more than 5mm)
　　　score 3; has stringing, shows the tack (1 ~ 5 mm)
　　　grade 2; slightly stringiness was observed, indicating the tack (1 ~ 5 mm)
　　　score 1; stringiness can not be seen, is less sticky
　(0 mm) (vii) heat sexual
　heat resistance test of the lubricating oil is usually carried out by adding an additive such as an antioxidant.
[0154]
　For each of the lubricating oil compositions of Examples and Comparative Examples were prepared heat resistance evaluation lubricating oil composition by adding dissolving 0.5% by weight of 2,6-di -tert- butyl -p- cresol.
[0155]
　Then, the sample was placed 40mL glass cylinder sample bottle 50 mL, was 500 hours of heat treatment using a 120 ° C. oven. Based on the change in color tone, it is determined that the color change is excellent small samples heat resistance.
[0156]
　The decision of the evaluation results, was carried out by scores of below.
[0157]
　　　Rating of 5; little change is not recognized color
　　　observed slight change in color tone, color change is observed to pale yellow; score 4
　　　score 3; color change is observed in the pale yellow
　　　score 2; color change is compared target increased, the color changes are observed to yellow
　　　score 1; large color change, color change to brown is observed
　example 2-1
　rapeseed oil (a-1) and the copolymer (B-1) preparative mass ratio to prepare a lubricating oil composition were mixed so that the 90/10. Results of evaluation of properties of the obtained lubricating oil compositions are shown in Table 3-1.
[0158]
　[Examples 2-2 to 2-8, Comparative Examples 2-1 to 2-4]
　were mixed according to Table 3-1 and 3-2, were prepared lubricating oil composition. The evaluation results are shown in Tables 3-1 and 3-2.
[0159]
　Example 2-9]
　rapeseed oil (A-1), copolymer (B-3) and copolymer (B-10), were mixed so that the mass ratio becomes 90/5/5 lubrication the oil composition was prepared. Evaluation results are shown in Table 3-2
　Example 2-10]
　using a synthetic polyol ester (A-3), were mixed in proportions according to Table 3-2, were prepared lubricating oil composition. The evaluation results are shown in Table 3-1.
[0160]
　[Example 2-11 to Example 2-16, Comparative Example 2-5]
　using a synthetic ester (DIDA) (A-2) , were mixed in proportions according to Table 3-3, the lubricating oil composition It was prepared. The evaluation results are shown in Table 3-3.
[0161]
　From Table 3-1 and 3-2, the composition of Comparative Example 2-4 using a copolymer containing no ricinoleic acid-derived structure, storage stability (compatibility), it can be seen that poor adhesion . Further, as compared with the composition of Comparative Example 2-3 using ricinoleic acid homopolymer, Examples 2-1 to 2-9 using the same base oil (A-1) are all excellent in heat resistance , in addition, the adhesive force is excellent.
[0162]
　Also, Table 3-3 using synthetic esters (A-2) a base oil, the kinematic viscosity (40 ° C.) 100 mm 2 Examples and Comparative Examples were formulated as (co) polymer is about / s which compares. From Table 3-3, Examples compared with compositions in Comparative Examples 2-5 using ricinoleic acid homopolymer it can be seen that both excellent shear stability. Furthermore, it is found a tendency that the intrinsic viscosity of the copolymer (B) used is excellent in low enough shear stability. In addition, many structural units derived from ricinoleic acid (a) (70 mol%) example using a copolymer containing it can be seen that excellent shear stability.
[0163]
[Table 3-1]

[0164]
[Table 3-2]

claims

[Claim 1]Following requirement (B1) satisfying ~ a (B3) copolymer
　(B): (B1) a structural unit derived from ricinoleic acid and (a),
　　　　　and the structural unit derived from an aliphatic dicarboxylic acid (b),
　　　　　the number of carbon atoms a constituent unit derived from a diol 2 ~ 10 (c)
including;
　(B2) the structural unit (a), (b) and when the total of 100 mol% of (c), the structural unit (a) content of 20 to 90 mol% of content of 5 to 40 mol% of the structural unit (b), the content of constituent units (c) is 5 to 40
　mol%; (B3) an intrinsic viscosity [IV] is It is in the range of 0.1 ~ 2.0dl / g.
[Claim 2]
　Base oil (A) and the mass of the copolymer of Claim 1 (B) and a, and the weight ratio of the base oil (A) and the copolymer (B) ((A) / mass of (B)) is a lubricating oil composition is 60/40 to 99.5 / 0.5.
[Claim 3]
　The lubricating oil composition of claim 2 wherein the base oil (A) is a vegetable and / or synthetic esters.
[Claim 4]
　Wherein the synthetic ester lubricating oil composition according to claim 3 is a diester or polyol ester.
[Claim 5]
　Wherein the synthetic ester lubricating oil composition according to claim 3 or 4 aliphatic diester or aliphatic polyol esters.
[Claim 6]
　In the requirement (B2), the molar ratio of the structural units (b) and the structural unit (c) ((b) / (c)) is 0.9-1.1, of claims 2-5 the lubricating oil composition according to any one.
[Claim 7]
　In the requirement (B2), the structural unit (a) is 40 to 90 mol%, the lubricating oil composition according to any one of claims 2-6.
[8.]
　In the above requirement (B3), an intrinsic viscosity [IV] is in the range of 0.3 ~ 1.5dl / g, the lubricating oil composition according to any one of claims 2-7.
[Claim 9]
　Antioxidants, extreme pressure agents, rust inhibitors, metal deactivators, antiwear additives, defoamers, detergent dispersant and at least one additive selected from the group consisting of pour point depressant and (C) the lubricating oil composition according to any one of claims 2-8, further comprising.
[Claim 10]
　The aliphatic dicarboxylic acid is sebacic acid, lubricating oil composition according to any one of claims 2-9.
[Claim 11]
　Diols of the 2 to 10 carbon atoms is 1,4-butanediol, lubricating oil composition according to any one of claims 2-10.
[Claim 12]
　Gear oil comprising a lubricating oil composition according to any one of claims 2 to 11.
[Claim 13]
　Hydraulic oil consisting of the lubricating oil composition according to any one of claims 2 to 11.
[Claim 14]
　Engine oil consisting of the lubricating oil composition according to any one of claims 2 to 11.
[Claim 15]
　Grease consisting lubricating oil composition according to any one of claims 2 to 11.
[16.]
　Machining oil consisting of the lubricating oil composition according to any one of claims 2 to 11.